CN104928740B - A kind of surface treatment method reducing Copper Foil hair side copper powder - Google Patents
A kind of surface treatment method reducing Copper Foil hair side copper powder Download PDFInfo
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Abstract
The invention provides a kind of processing method reducing Copper Foil hair side copper powder, the hair paper tinsel electroplating foil passes sequentially through the 1st roughening operation, the 2nd roughening operation, the 1st curing process, the 2nd curing process, zinc-plated operation, anti-oxidation operation, coupling agent painting process, baking operation process.By the treatment process of the present invention, a large amount of generations reducing copper powder, Copper Foil 10cm2In sample, copper powder quantity is less than 10, and maximum copper powder diameter is less than 30 μm, significantly reduces it and causes short-circuit risk during making printed circuit board.
Description
Technical field
The present invention relates to a kind of surface treatment method reducing Copper Foil hair side copper powder.
Background technology
The Copper Foil that existing Copper Foil production technology produces, due to the crystalline structure of hair side deposition in surface treatment coarsening process
Structure is very loose, is easily formed more copper powder, and more copper powder or copper powder diameter, more than 50 μm, are making printed circuit board
During occur that the risk of short circuit is very high, when Copper Foil hair side copper powder quantity is more, can cause Copper Foil after the client of downstream
In process, circuit is breakdown or short-circuit, has a strong impact on the quality of product.
With the fast development of printed circuit board industry, the miniaturization of electronic devices and components and printed circuit board fine
Changing, the short circuit risk that more hair side copper powder causes is more and more higher.
Existing technical scheme cannot effectively solve the more problem of hair side copper powder, generally uses regulation roughening, solidification electricity
Stream, reduces copper powder and produces.Copper powder can only be suppressed to a certain extent to produce, DeGrain, it is impossible to fundamentally effectively solve
Hair side copper powder, 10cm2Having copper powder quantity 20-30 in sample, maximum copper powder diameter 40-60 μm is in the majority.
Content of the invention
It is an object of the invention to provide a kind of surface treatment method reducing Copper Foil hair side copper powder, the surface treatment of the present invention
Method fundamentally can effectively reduce Copper Foil hair side copper powder.
The present invention is achieved by the following technical solutions: a kind of processing method reducing Copper Foil hair side copper powder, by foil
The hair paper tinsel electroplated pass sequentially through the 1st roughening operation, the 2nd roughening operation, the 1st curing process, the 2nd curing process, zinc-plated operation,
Anti-oxidation operation, coupling agent painting process, baking operation process, the concrete operations of step are as follows:
(1) the 1st roughening operation: the hair paper tinsel that foil is electroplated, in temperature 20-50 DEG C, under the conditions of preferably 25-35 DEG C,
Containing sulfuric acid concentration 150-250g/L, preferably 180-220g/L, Cu2+Coarsening solution (the roughening of concentration 5-20g/L, preferably 8-14g/L
Liquid component is copper sulphate and sulfuric acid, wherein Cu2+Refer to the concentration of copper sulphate.Electroplating in), electroplating one section of current density is
20-50A/dm2, preferably 24-40A/dm2, electroplating two sections of current densities is 3-12A/dm2, preferably 5-9A/dm2；
(2) the 2nd roughening operations: the Copper Foil that will process through the 1st roughening operation, in temperature 20-50 DEG C, preferably 25-35 DEG C bar
Under part, containing sulfuric acid concentration 150-250g/L, preferably 180-220g/L, Cu2+The roughening of concentration 5-20g/L, preferably 8-14g/L
Electroplating in liquid, electroplating one section of current density is 15-40A/dm2, preferably 18-30A/dm2, electroplating two sections of current densities is 3-
12A/dm2, preferably 4-7A/dm2；
(3) the 1st curing process: the Copper Foil that will process through the 2nd roughening operation, in temperature 20-50 DEG C, preferably 30-45 DEG C bar
Under part, containing sulfuric acid concentration 80-150g/L, preferably 90-140g/L, Cu2+Concentration 30-90g/L, preferably 50-60g/L, HCl are dense
Degree 5-30ppm, preferably 10-15ppm, low molecular weight gelatine 100-500ppm, preferably 200-300ppm (below molecular weight 10000)
Solidification liquid in electroplate, electroplate one section of current density 15-40A/dm2, preferably 18-30A/dm2, electroplate two sections of current densities
15-40A/dm2, preferably 18-30A/dm2；
(4) the 2nd curing process: the Copper Foil that will process through the 1st curing process, under the conditions of temperature 30-45 DEG C, containing sulphur
Acid concentration 80-150g/L, preferably 90-140g/L, Cu2+Concentration 30-90g/L, preferably 50-60g/L, HCl concentration 5-30ppm, excellent
Select 10-15ppm, low molecular weight gelatine 100-500ppm, preferably 200-300ppm (below molecular weight 10000, preferably 2000～
10000, preferably 5000～10000) solidification liquid is electroplated, electroplates one section of current density 15-40A/dm2, preferably 18-
30A/dm2, electroplate two sections of current densities 15-40A/dm2, preferably 18-30A/dm2；
(5) zinc-plated operation: the Copper Foil that will process through the 2nd curing process, in temperature 30-55 DEG C, preferably 40-45 DEG C, pH value
7.5-11, preferably under conditions of 8-10, containing Zn2+Concentration (such as zinc sulfate) 2.0-10.0g/L, preferably 3.0-8.0g/L,
Potassium pyrophosphate concentration 40-100g/L, electroplates in preferably 50-80g/L galvanizing flux, one section of current density of the Copper Foil hair side of electroplating operations
0.5-2.0A/dm2, preferably 0.6-1.4A/dm2, two sections of current densities are 0.5-2.0A/dm2, preferably 0.6-1.4A/dm2, light face
Current density is 1.0-3.0A/dm2, preferably 1.2-2.5A/dm2；
(6) anti-oxidation operation: the Copper Foil that will process through zinc-plated operation, in temperature 20-50 DEG C, preferably 25-40 DEG C, pH value 9-
13, preferably under conditions of 10-12, containing Cr6+Concentration 0.8～2.0g/L (such as potassium bichromate), preferably 1.0-1.5g/L, anti-
Oxidation solution is electroplated, one section of current density 3-10A/dm of the Copper Foil hair side of electroplating operations2, preferably 4-8A/dm2, two sections of current densities
For 1.0-3.0A/dm2, preferably 1.2-2.5A/dm2, light surface current density is 1.0-3.0A/dm2, preferably 1.2-2.5A/dm2；
(7) coupling agent painting process: after the copper foil water washing after electroplating anti-oxidation operation, sprays organic film coupling agent, spray
Applying temperature is 10-50 DEG C, and preferably 25-35 DEG C, the concentration of described organic film coupling agent (silane coupler) is 1.0-5.0g/L, excellent
Select 1.5-3.5g/L；
(8) baking step: after above-mentioned operation completes, dries, and dries temperature 200-320 DEG C, preferably 220-300 DEG C, dry
Rear optional rolling, rolling speed is such as 15-25m/min.
Copper Foil 10cm after process2In sample, copper powder quantity is less than 10, and maximum copper powder diameter is less than 30 μm.
Coupling agent is usually silane coupler, can be commercially available silane coupler, the such as silane with vinyl, as
Vinyl trichlorosilane, VTES, γ-glycidylpropyl-trimethoxy silane etc..
In this application, as shown in Figure 2 the 1st roughening groove, the 2nd roughening groove, the 1st solidification groove, the 2nd solidification groove in left and right sides each
Have 1 piece of positive plate, galvanizing bath and anti-oxidation tank left and right sides to be respectively arranged with 1 piece of positive plate, centre is respectively arranged with 1 piece of positive plate, through left side sun
Pole plate for one section of current density, through grading electrode plate for light surface current density, through the right positive plate for two sections of electricity
Current density.
In this application, Cu2+Concentration refers to the concentration of copper sulphate.
Advantages of the present invention:
By the specially treated operation of the present invention, with the addition of in solidification liquid in copper foil surface solidification process further
HCl and the curing additive of low molecular weight gelatine (below molecular weight 10000), curing additive increases in Copper Foil solidification process
Cathodic polarization effect, makes the small copper crystal grain in solidification process go to fill roughening operation and forms the hole in loose thick deposit
Gap, makes the copper crystal grain loosening solidification and Copper Foil form firm entirety, reduces the generation of copper powder, Copper Foil 10cm2Copper powder number in sample
Amount is less than 10, and maximum copper powder diameter is less than 30 μm.
Brief description
Fig. 1 is the flow chart of the inventive method.
Fig. 2 is from the 1st roughening operation to anti-oxidation technical process schematic diagram.
Wherein 1 for Copper Foil, 2 for positive plate, 3 for rubber roll, 4 be liquid level, 11 is the 1st roughening treatment groove, 12 be the 1st washing
Groove, 13 is the 2nd roughening treatment groove, and 14 is the 2nd rinsing bowl, and 15 is the 1st solidification groove, and 16 is the 3rd rinsing bowl, and 17 is the 2nd solidification groove,
18 is the 4th rinsing bowl, and 19 is galvanizing bath, and 20 is the 5th rinsing bowl, and 21 is anti-oxidation treatment trough.
Detailed description of the invention
Below by way of specific embodiment, the present invention is described.
In an embodiment, as it is shown in figure 1, carry out the 1st roughening treatment in the 1st roughening treatment groove 11, in the 2nd roughening treatment
Groove 13 carries out the 2nd roughening treatment, in the 1st solidification groove 15, carries out the 1st solidification process, in the 2nd solidification groove 17, carry out the 2nd solid
Change process, carries out zinc-plated process in galvanizing bath 19, carries out anti-oxidation process in anti-oxidation treatment trough 21, these operations it
Between, carry out at washing in the 1st rinsing bowl the 12nd, the 2nd rinsing bowl the 14th, the 3rd rinsing bowl the 16th, the 4th rinsing bowl the 18th, the 5th rinsing bowl 20
Reason.
Embodiment 1:
1st, the 1st roughening operation: after the hair paper tinsel that generate foil operation, electroplate in coarsening solution, the one of electroplating operations
Section current density is 24A/dm2, two sections of current densities are 5A/dm2, coarsening solution temperature controls at 30 DEG C, and in coarsening solution, sulfuric acid is dense
Degree is 200g/L, Cu2+Concentration be 10g/L.
2nd, the 2nd roughening operation: the Copper Foil after the 1st roughening operation plating is electroplated in coarsening solution, a section of electroplating operations
Current density is 18A/dm2, two sections of current densities are 4A/dm2, coarsening solution temperature controls at 30 DEG C, the concentration of sulfuric acid in coarsening solution
For 200g/L, Cu2+Concentration be 10g/L.
3rd, the 1st curing process: by the Copper Foil plating in solidification liquid after the 2nd roughening operation plating, a section of electroplating operations
Current density is 18A/dm2, two sections of current densities are 18A/dm2, solidification liquid temp controls at 30 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 100g/L, and the concentration of bivalent cupric ion is 50g/L, also includes curing additive in solidification liquid, and curing additive is included in
The hydrochloric acid of the 10ppm concentration in solidification liquid, low molecular weight gelatine (below molecular weight 10000) 200ppm.
4th, the 2nd curing process: by the Copper Foil plating in solidification liquid after the 1st curing process plating, a section of electroplating operations
Current density is 18A/dm2, two sections of current densities are 18A/dm2, solidification liquid temp controls at 35 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 100g/L, and the concentration of bivalent cupric ion is 50g/L, also includes curing additive in solidification liquid, and curing additive is included in
The hydrochloric acid of the 10ppm concentration in solidification liquid, low molecular weight gelatine (below molecular weight 10000) 200ppm.
5th, zinc-plated operation: the Copper Foil after the 2nd curing process plating is electroplated in galvanizing flux, the Copper Foil hair side of electroplating operations
One section of current density is 0.8A/dm2, two sections of current densities are 0.8A/dm2, light surface current density is 1.5A/dm2, zinc-plated liquid temperature
Degree controls at 40 DEG C, and pH value is 8.5, Zn in galvanizing flux2+Concentration is 4.0g/L, and potassium pyrophosphate concentration is 50g/L.
6th, anti-oxidation operation: the Copper Foil after electroplating zinc-plated operation is electroplated in anti-oxidation liquid, the Copper Foil hair of electroplating operations
One section of face current density is 4A/dm2, two sections of current densities are 1.5A/dm2, light surface current density is 1.5A/dm2, anti-oxidation liquid
Temperature controls at 30 DEG C, and pH value is 11.0, Cr in anti-oxidation liquid6+Concentration is 1.0g/L.As shown in Figure 2 galvanizing bath and anti-oxidation in
Left, center, right is respectively arranged with 1 piece of positive plate, through left side positive plate for one section of current density, through grading electrode plate for light surface current
Density, through the right positive plate for two sections of current densities.
7th, coupling agent spraying process: after the copper foil water washing after electroplating anti-oxidation operation, sprays organic film coupling agent, spraying
Temperature is 25 DEG C, and the concentration of described organic film coupling agent is 2.5g/L；
8th, after above-mentioned operation completes, dry rolling, dry temperature 260 DEG C, rolling speed 20m/min.
Copper Foil 10cm after process2Copper powder quantity 8 in sample, maximum copper powder diameter 25 μm.
Embodiment 2:
1st, the 1st roughening operation: after the hair paper tinsel that generate foil operation, electroplate in coarsening solution, the one of electroplating operations
Section current density is 30A/dm2, two sections of current densities are 8A/dm2, coarsening solution temperature controls at 35 DEG C, and in coarsening solution, sulfuric acid is dense
Degree is 220g/L, Cu2+Concentration be 14g/L.
2nd, the 2nd roughening operation: the Copper Foil after the 1st roughening operation plating is electroplated in coarsening solution, a section of electroplating operations
Current density is 20A/dm2, two sections of current densities are 5A/dm2, coarsening solution temperature controls at 35 DEG C, the concentration of sulfuric acid in coarsening solution
For 220g/L, Cu2+Concentration be 14g/L.
3rd, the 1st curing process: by the Copper Foil plating in solidification liquid after the 2nd roughening operation plating, a section of electroplating operations
Current density is 25A/dm2, two sections of current densities are 25A/dm2, solidification liquid temp controls at 35 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 120g/L, Cu2+Concentration is 60g/L, also includes curing additive in solidification liquid, and curing additive is included in solidification liquid
The hydrochloric acid of 15ppm concentration, low molecular weight gelatine (below molecular weight 10000) 250ppm.
4th, the 2nd curing process: by the Copper Foil plating in solidification liquid after the 1st curing process plating, a section of electroplating operations
Current density is 25A/dm2, two sections of current densities are 25A/dm2, solidification liquid temp controls at 35 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 120g/L, Cu2+Concentration is 60g/L, also includes curing additive in solidification liquid, and curing additive is included in solidification liquid
The hydrochloric acid of 15ppm concentration, low molecular weight gelatine (below molecular weight 10000) 250ppm.
5th, zinc-plated operation: the Copper Foil after the 2nd curing process plating is electroplated in galvanizing flux, the Copper Foil hair side of electroplating operations
One section of current density is 1.4A/dm2, two sections of current densities are 1.4A/dm2, light surface current density is 2.0A/dm2, zinc-plated liquid temperature
Degree controls at 45 DEG C, and pH value is 10.0, Zn in galvanizing flux2+Concentration is 6.0g/L, and potassium pyrophosphate concentration is 70g/L.
6th, anti-oxidation operation: the Copper Foil after electroplating zinc-plated operation is electroplated in anti-oxidation liquid, the Copper Foil hair of electroplating operations
One section of face current density is 8A/dm2, two sections of current densities are 2.0A/dm2, light surface current density is 2.0A/dm2, anti-oxidation liquid
Temperature controls at 35 DEG C, and pH value is 11.5, Cr in anti-oxidation liquid6+Concentration is 1.5g/L.
7th, after the copper foil water washing after electroplating anti-oxidation operation, spraying organic film coupling agent, spraying temperature is 30 DEG C, described
The concentration of organic film coupling agent is 2.0g/L；
8th, after above-mentioned operation completes, dry rolling, dry temperature 230 DEG C, rolling speed 22m/min.
Copper Foil 10cm after process2Sample in copper powder quantity 9, maximum copper powder diameter 20 μm
Embodiment 3:
1st, the 1st roughening operation: after the hair paper tinsel that generate foil operation, electroplate in coarsening solution, the one of electroplating operations
Section current density is 35A/dm2, two sections of current densities are 9A/dm2, coarsening solution temperature controls at 25 DEG C, and in coarsening solution, sulfuric acid is dense
Degree is 190g/L, Cu2+Concentration be 12g/L.
2nd, the 2nd roughening operation: the Copper Foil after the 1st roughening operation plating is electroplated in coarsening solution, a section of electroplating operations
Current density is 25A/dm2, two sections of current densities are 7A/dm2, coarsening solution temperature controls at 25 DEG C, the concentration of sulfuric acid in coarsening solution
For 190g/L, Cu2+Concentration be 12g/L.
3rd, the 1st curing process: by the Copper Foil plating in solidification liquid after the 2nd roughening operation plating, a section of electroplating operations
Current density is 30A/dm2, two sections of current densities are 30A/dm2, solidification liquid temp controls at 40 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 140g/L, Cu2+Concentration is 55g/L, also includes curing additive in solidification liquid, and curing additive is included in solidification liquid
The hydrochloric acid of 12ppm concentration, low molecular weight gelatine (below molecular weight 10000) 300ppm.
4th, the 2nd curing process: by the Copper Foil plating in solidification liquid after the 1st curing process plating, a section of electroplating operations
Current density is 30A/dm2, two sections of current densities are 30A/dm2, solidification liquid temp controls at 40 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 140g/L, Cu2+Concentration is 55g/L, also includes curing additive in solidification liquid, and curing additive is included in solidification liquid
The hydrochloric acid of 12ppm concentration, low molecular weight gelatine (below molecular weight 10000) 300ppm.
5th, zinc-plated operation: the Copper Foil after the 2nd curing process plating is electroplated in galvanizing flux, the Copper Foil hair side of electroplating operations
One section of current density is 1.2A/dm2, two sections of current densities are 1.2A/dm2, light surface current density is 2.3A/dm2, zinc-plated liquid temperature
Degree controls at 42 DEG C, and pH value is 8.0, Zn in galvanizing flux2+Concentration is 8.0g/L, and potassium pyrophosphate concentration is 80g/L.
6th, anti-oxidation operation: the Copper Foil after electroplating zinc-plated operation is electroplated in anti-oxidation liquid, the Copper Foil hair of electroplating operations
One section of face current density is 5A/dm2, two sections of current densities are 2.1A/dm2, light surface current density is 2.2A/dm2, anti-oxidation liquid
Temperature controls at 40 DEG C, and pH value is 12.0, Cr in anti-oxidation liquid6+Concentration is 1.4g/L.
7th, after the copper foil water washing after electroplating anti-oxidation operation, spraying organic film coupling agent, spraying temperature is 35 DEG C, described
The concentration of organic film coupling agent is 1.8g/L；
8th, after above-mentioned operation completes, dry rolling, dry temperature 250 DEG C, rolling speed 18m/min.
Copper Foil 10cm after process2Copper powder quantity 5 in sample, maximum copper powder diameter 15 μm.
Embodiment 4:
1st, the 1st roughening operation: after the hair paper tinsel that generate foil operation, electroplate in coarsening solution, the one of electroplating operations
Section current density is 40A/dm2, two sections of current densities are 8A/dm2, coarsening solution temperature controls at 32 DEG C, and in coarsening solution, sulfuric acid is dense
Degree is 210g/L, Cu2+Concentration be 9g/L.
2nd, the 2nd roughening operation: the Copper Foil after the 1st roughening operation plating is electroplated in coarsening solution, a section of electroplating operations
Current density is 28A/dm2, two sections of current densities are 6A/dm2, coarsening solution temperature controls at 32 DEG C, the concentration of sulfuric acid in coarsening solution
For 210g/L, Cu2+Concentration be 9g/L.
3rd, the 1st curing process: by the Copper Foil plating in solidification liquid after the 2nd roughening operation plating, a section of electroplating operations
Current density is 27A/dm2, two sections of current densities are 27A/dm2, solidification liquid temp controls at 38 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 115g/L, Cu2+Concentration is 58g/L, also includes curing additive in solidification liquid, and curing additive is included in solidification liquid
The hydrochloric acid of 13ppm concentration, low molecular weight gelatine (below molecular weight 10000) 260ppm.
4th, the 2nd curing process: by the Copper Foil plating in solidification liquid after the 1st curing process plating, a section of electroplating operations
Current density is 27A/dm2, two sections of current densities are 27A/dm2, solidification liquid temp controls at 38 DEG C, and in solidification liquid, sulfuric acid is dense
Degree is 115g/L, Cu2+Concentration is 58g/L, also includes curing additive in solidification liquid, and curing additive is included in solidification liquid
The hydrochloric acid of 13ppm concentration, low molecular weight gelatine (below molecular weight 10000) 260ppm.
5th, zinc-plated operation: the Copper Foil after the 2nd curing process plating is electroplated in galvanizing flux, the Copper Foil hair side of electroplating operations
One section of current density is 0.9A/dm2, two sections of current densities are 0.9A/dm2, light surface current density is 1.8A/dm2, zinc-plated liquid temperature
Degree controls at 43 DEG C, and pH value is 8.9, Zn in galvanizing flux2+Concentration is 6.0g/L, and potassium pyrophosphate concentration is 70g/L.
6th, anti-oxidation operation: the Copper Foil after electroplating zinc-plated operation is electroplated in anti-oxidation liquid, the Copper Foil hair of electroplating operations
One section of face current density is 6A/dm2, two sections of current densities are 1.8A/dm2, light surface current density is 2.0A/dm2, anti-oxidation liquid
Temperature controls at 38 DEG C, and pH value is 11.5, Cr in anti-oxidation liquid6+Concentration is 1.2g/L.
7th, after the copper foil water washing after electroplating anti-oxidation operation, spraying organic film coupling agent, spraying temperature is 30 DEG C, described
The concentration of organic film coupling agent is 2.6g/L；
8th, after above-mentioned operation completes, dry rolling, dry temperature 280 DEG C, rolling speed 25m/min.
Copper Foil 10cm after process2Copper powder quantity 3 in sample, maximum copper powder diameter 18 μm.
Comparative example 1
Carry out similarly to Example 1, simply the solidification liquid in the 1st program curing and the 2nd program curing not hydrochloric and
Low molecular weight gelatine.Copper Foil 10cm after process2Copper powder quantity 31 in sample, maximum copper powder diameter 27 μm.
Comparative example 2
Carrying out similarly to Example 1, simply the solidification liquid in the 1st program curing and the 2nd program curing includes 50ppm salt
Acid and 700ppm low molecular weight gelatine.Copper Foil 10cm after process2Copper powder quantity 18 in sample, maximum copper powder diameter 26 μm.
As can be seen from the above embodiments, the Copper Foil 10cm after being processed by the present invention2In sample, copper powder quantity is less than
10, maximum copper powder diameter is less than 30 μm.
The process of surface treatment of the present invention, is made the tiny copper crystal grain of solidification in the curing process by adding curing additive
Fill the hole in the loose thick deposit that roughening is formed, make the copper crystal grain loosening solidification form firm entirety with Copper Foil, from
Fundamentally reduce the generation of copper powder, Copper Foil 10cm in a large number2In sample, copper powder quantity is less than 10, and maximum copper powder diameter is less than
30 μm, significantly reduce it and cause short-circuit risk during making printed circuit board.
Claims (5)
1. reducing a processing method for Copper Foil hair side copper powder, the method includes:
(1) the 1st roughening operation: the hair paper tinsel electroplating foil, under conditions of temperature 20-50 DEG C, containing sulfuric acid concentration
150-250g/L、Cu2+Electroplating in the coarsening solution of concentration 5-20g/L, electroplating one section of current density is 20-50A/dm2, plating
Two sections of current densities are 3-12 A/dm2；
(2) the 2nd roughening operations: the Copper Foil that will process through the 1st roughening operation, under conditions of temperature 20-50 DEG C, containing sulfuric acid
Concentration 150-250g/L, Cu2+Electroplating in the coarsening solution of concentration 5-20g/L, electroplating one section of current density is 15-40A/dm2,
Electroplating two sections of current densities is 3-12 A/dm2；
(3) the 1st curing process: the Copper Foil that will process through the 2nd roughening operation, under conditions of temperature 20-50 DEG C, containing sulfuric acid
Concentration 80-150 g/L, Cu2+Concentration 30-90g/L, HCl concentration 5-30ppm, low molecular weight gelatine below 10000 for the molecular weight
The solidification liquid of 100-500ppm is electroplated, electroplates one section of current density 15-40A/dm2, electroplate two sections of current densities 15-
40A/dm2；
(4) the 2nd curing process: the Copper Foil that will process through the 1st curing process, under the conditions of temperature 30-45 DEG C, dense containing sulfuric acid
Degree 80-150 g/L, Cu2+Concentration 30-90g/L, HCl concentration 5-30ppm, the molecular weight low molecular weight gelatine 100-below 10000
The solidification liquid of 500ppm is electroplated, electroplates one section of current density 15-40A/dm2, electroplate two sections of current densities 15-40A/
dm2；
(5) zinc-plated operation: the Copper Foil that will process through the 2nd curing process, under conditions of temperature 30-55 DEG C, pH value 7.5-11,
Containing Zn2+Concentration 2.0-10.0g/L, potassium pyrophosphate concentration 40-100g/L galvanizing flux in plating, the Copper Foil hair side of electroplating operations
One section of current density 0.5-2.0 A/dm2, two sections of current densities are 0.5-2.0 A/dm2, light surface current density is 1.0-3.0A/
dm2；
(6) anti-oxidation operation: the Copper Foil that will process through zinc-plated operation, under conditions of temperature 20-50 DEG C, pH value 9-13, is containing
There is Cr6+The anti-oxidation liquid of concentration 0.8 ~ 2.0g/L is electroplated, one section of current density 3-10 A/dm of the Copper Foil hair side of electroplating operations2,
Two sections of current densities are 1.0-3.0 A/dm2, light surface current density is 1.0-3.0 A/dm2；
(7) coupling agent painting process: after the copper foil water washing after electroplating anti-oxidation operation, sprays organic film coupling agent, spraying temperature
Degree is 10-50 DEG C, and the concentration of described organic film coupling agent is 1.0-5.0g/L；
(8) baking step: after above-mentioned operation completes, dries, and dries temperature 200-320 DEG C, optional rolling after drying.
2. foil wherein, in step (1) the 1st roughening operation, is electroplated by processing method according to claim 1
Hair paper tinsel, under the conditions of temperature 25-35 DEG C, containing sulfuric acid concentration 180-220 g/L, Cu2+The coarsening solution of concentration 8-14g/L enters
Row plating, electroplating one section of current density is 24-40A/dm2, electroplating two sections of current densities is 5-9A/dm2；
In step (2) the 2nd roughening operation, will contain under the conditions of temperature 25-35 DEG C through the Copper Foil of the 1st roughening operation process
Have sulfuric acid concentration 180-220 g/L, Cu2+Electroplating in the coarsening solution of concentration 8-14g/L, electroplating one section of current density is 18-
30A/dm2, electroplating two sections of current densities is 4-7A/dm2；
In step (3) the 1st curing process, will contain under the conditions of temperature 30-45 DEG C through the Copper Foil of the 2nd roughening operation process
Have sulfuric acid concentration 90-140 g/L, Cu2+Concentration 50-60g/L, HCl concentration 10-15ppm, low molecule below 10000 for the molecular weight
The solidification liquid of amount gelatin 200-300ppm is electroplated, electroplates one section of current density 18-30A/dm2, electroplate two sections of electric currents close
Degree 18-30A/dm2；
In step (4) the 2nd curing process, will contain under the conditions of temperature 30-45 DEG C through the Copper Foil of the 1st curing process process
Have sulfuric acid concentration 90-140 g/L, Cu2+Concentration 50-60g/L, HCl concentration 10-15ppm, low molecule below 10000 for the molecular weight
The solidification liquid of amount gelatin 200-300ppm is electroplated, electroplates one section of current density 18-30A/dm2, electroplate two sections of electric currents close
Degree 18-30A/dm2；
In the zinc-plated operation of step (5), will be through the Copper Foil of the 2nd curing process process, at the bar of temperature 40-45 DEG C, pH value 8-10
Under part, containing Zn2+Concentration 3.0-8.0g/L, potassium pyrophosphate concentration 50-80g/L galvanizing flux in plating, the copper of electroplating operations
One section of current density 0.6-1.4A/dm of paper tinsel hair side2, two sections of current densities are 0.6-1.4A/dm2, light surface current density is 1.2-
2.5A/dm2；
In the anti-oxidation operation of step (6), the Copper Foil that will process through zinc-plated operation, at the bar of temperature 25-40 DEG C, pH value 10-12
Under part, containing Cr6+The anti-oxidation liquid of concentration 1.0-1.5g/L is electroplated, one section of current density 4-of the Copper Foil hair side of electroplating operations
8A/dm2, two sections of current densities are 1.2-2.5A/dm2, light surface current density is 1.2-2.5A/dm2；
In step (7) coupling agent painting process, spraying temperature is 25-35 DEG C, and the concentration of described organic film coupling agent is 1.5-
3.5g/L；
In step (8) baking step, drying temperature is 220-300 DEG C, and the rolling speed after drying is 15-25m/min.
3. processing method according to claim 1 and 2, wherein, Copper Foil 10cm after process2In sample, copper powder quantity does not surpasses
Crossing 10, maximum copper powder diameter is less than 30 μm.
4. processing method according to claim 1 and 2, wherein, in galvanizing bath and anti-oxidation tank, left, center, right is respectively arranged with 1 piece of anode
Plate, through left side positive plate for one section of current density, through grading electrode plate for light surface current density, through the right anode
Plate for two sections of current densities.
5. processing method according to claim 3, wherein, in galvanizing bath and anti-oxidation tank, left, center, right is respectively arranged with 1 piece of positive plate,
Through left side positive plate for one section of current density, through grading electrode plate for light surface current density, through the right positive plate
For two sections of current densities.
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| CN105154927A (en) * | 2015-10-19 | 2015-12-16 | 无锡清杨机械制造有限公司 | Electrolytic copper foil surface treatment process |
| CN106086973A (en) * | 2016-06-03 | 2016-11-09 | 安徽铜冠铜箔有限公司 | A kind of process of surface treatment of black electronic Copper Foil |
| CN106011965B (en) * | 2016-06-13 | 2018-08-14 | 山东金宝电子股份有限公司 | A kind of fine roughening treatment technique of electrolytic copper foil surface |
| CN105970261A (en) * | 2016-06-14 | 2016-09-28 | 安徽铜冠铜箔有限公司 | Chrome-free treatment technology preventing surface oxidation of copper foil |
| CN106225449B (en) * | 2016-06-25 | 2018-06-12 | 宁波恒进自动化技术有限公司 | The method of copper foil surface adherency copper powder when eliminating copper foil cutting |
| CN106521564A (en) * | 2016-10-27 | 2017-03-22 | 建滔（连州）铜箔有限公司 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| CN110952119B (en) * | 2019-11-28 | 2021-07-30 | 九江德福科技股份有限公司 | Surface roughening method applied to high-frequency high-speed electrolytic copper foil |
| CN113718307B (en) * | 2021-06-16 | 2023-09-15 | 惠州合正电子科技有限公司 | Surface treatment process for high-peel-resistance copper foil |
| CN113564651B (en) * | 2021-09-24 | 2021-12-14 | 江东电子材料有限公司 | Copper foil and processing method thereof |
| CN114990654B (en) * | 2022-06-02 | 2024-04-26 | 山东金宝电子有限公司 | Electrolytic copper foil surface treatment process, HVLP copper foil product and application thereof |
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| CN104674316A (en) * | 2015-02-12 | 2015-06-03 | 安徽铜冠铜箔有限公司 | Treatment technique for enhancing peel strength of electronic copper foil |
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Address after: 247000 No. 189 Qingxi Road, Chizhou economic and Technological Development Zone, Anhui Co-patentee after: Hefei Tongguan electronic copper foil Co., Ltd Patentee after: Anhui Tongguan copper foil Group Co., Ltd Address before: 247000 No. 189 Qingxi Road, Chizhou economic and Technological Development Zone, Anhui Co-patentee before: HEFEI TONGGUAN GUOXUAN COPPER PRODUCTS Co.,Ltd. Patentee before: ANHUI TONGGUAN COPPER FOIL Co.,Ltd. |
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